Han Ting, Zhang Yun, He Benzhao, Lam Jacky W Y, Tang Ben Zhong
HKUST-Shenzhen Research Institute, No. 9 Yuexing 1st RD, South Area, Hi-tech Park, Nanshan, Shenzhen 518057, China.
Department of Chemistry, The Hong Kong Branch of Chinese National Engineering Research Center for Tissue Restoration and Reconstruction, Institute for Advanced Study, Department of Chemical and Biological Engineering and Division of Life Science, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, China.
Polymers (Basel). 2018 Jul 25;10(8):821. doi: 10.3390/polym10080821.
The development of polymeric materials with novel structures and unique properties and functionalities is of both academic and industrial significance. In this work, functional poly(dihalopentadiene)s were synthesized by boron trihalide-mediated multicomponent polymerization routes in a stereoselective manner. The polymerizations of tetraphenylethylene-containing diyne, BX₃ (X = Cl, Br) and -tolualdehyde proceed smoothly in dichloromethane under mild conditions to afford high molecular weight poly(dihalopentadiene)s with a predominant (,)-configuration in moderate to good yields. The reaction conditions and the boron trihalide used were found to have great effects on the stereochemistry of the resulting polymer structures. The obtained poly(1,5-dihalo-(,)-1,4-pentadiene)s possess high thermal stability and good film-forming ability. Their thin films show high refractive index of 1.9007⁻1.6462 in a wide wavelength region of 380⁻890 nm with low optical dispersion. The polymers are weakly emissive in dilute solutions but become highly emissive upon aggregated, demonstrating a unique phenomenon of aggregation-enhanced emission. Their nanoaggregates in aqueous media can serve as sensitive fluorescent chemosensors for the detection of explosives with a superamplification effect and a low detection limit.
开发具有新颖结构、独特性能和功能的聚合物材料具有重要的学术和工业意义。在本工作中，通过三卤化硼介导的多组分聚合路线以立体选择性方式合成了功能性聚（二卤代戊二烯）。含四苯乙烯的二炔、BX₃（X = Cl、Br）和对甲苯甲醛在温和条件下于二氯甲烷中顺利进行聚合反应，以中等至良好的产率得到具有主要（，）-构型的高分子量聚（二卤代戊二烯）。发现反应条件和所用的三卤化硼对所得聚合物结构的立体化学有很大影响。所得到的聚（1,5-二卤代-（，）-1,4-戊二烯）具有高的热稳定性和良好的成膜能力。它们的薄膜在380⁻890 nm的宽波长区域显示出1.9007⁻1.6462的高折射率，且具有低光学色散。这些聚合物在稀溶液中发射较弱，但聚集后会变得高度发射，表现出独特的聚集增强发射现象。它们在水性介质中的纳米聚集体可作为灵敏的荧光化学传感器用于检测爆炸物，具有超放大效应和低检测限。
